Anthraquinone dyestuffs and their application



Patented Sept. 25, 1934 LE A 1,975,061 ANTHRAQUINONE DYESTUFFS AND THEIR APPLICATION 4 Nor-man Hult'on Haddock, Frank Lodge, and

Colin Henry Lumsden, Blackley, Manchester, England, assignors to Imperial Chemical Q dustries Limited, a jig, firitain. c.

corporation of Great -No-Drawing.lApplication September 11, 1933, Serial No."68-9,044. In Great Britain September 11mins (01.260-) v -.box-y-'diphenyl-disu1fide;

This invention relates to the manufacture of new anthraquinone dyestuffs adapted to give iast d inesss eqia y on anima fibe :Acsn d h t9 t i tihv h hh W i an 'aminoeanthraquinone :ora k derivative thereof with the acid halideof a dinitro -diaryl-disulfide- .d e bpxv i a id w ich the initro sw m a e in ortho position to the SS- linkage, or with the acid itself, in the presence of an apn o ma e agen ran y e reduc fil fi ll ldQ- .tairied to the corresponding, ortho-aminomep .captan, wh c i t n tr a d wi e h gemacetic acidi give an ,orthoeamino-thioglycollic a id- Alternative w red c h d hitr -q a qy rdisu fi j-d q ox li a i to theQ0rrs h i e mthc -V am ne mer eptw .a y ee hoxylih; a i treat vthis w th helqsshp-ect e a id nd 7 hydrate th roduct in the la tam orm; h so-obtained lactam carboxylic acid; is used for l tinst th am nlqv-an hr qu n t acyl-amino-anthraguinone obtained is then hydrolyzed (delactaini'zed). The operations may be represented by the followingequations:

(H5O oHHoIoz) stituted anthraquinone and the other symbols haYeth in wal-si nificance; 1

The new dyestuffs may'beap'p lied .to the fiber, to giv its .dye n th ni lr ad indicated in copending"applicat ons s eirialfNos. 607,008 and 641,114. l I

As examples of "dinitro-di'aryl disulfid-dicarboxylic acids which'may Jae-used according to heintentihe we me 9 9.5 ZFQ ll PPQ-lA'" 1 b boxy-diphenyl-disulfide; 2,2 g1initr ,5';qicar ethoxy- 4A-dicarboxy dipheriyl disulflde';- and {2 ,2 -dini.tro 6 ,6' dicarboxy diphenyl'di'sulphide. It will be clear, however, that any other dicar 'boxy-dinitro-diaryl-disulfide of the "benzene,

2,25- dinitro 5,5, 1.

naphthalene or anthracene series may be em; 1

played; As'amino-anthraquinqneswhich maybe used we instance those mentioned in British Spec ification No. 2702/09, the more complex vcom pounds obtained by v debenzoyla'ting the Y dyes dcscribed in British specification 1T029352/10, and the amino-anthraquinone acridones'and amino anthraquinone tiiioxanthdnesl It will be clear thus that our invention includes "com pounds which contain but one anthraquinone nucleus which is substituted by one/ or more substituents of the form V NH: .NH?C O-ary1 son, as well aslcompounds which contain more than one anthraquinone nucleus, each of vWhich-or only one of which may carry a substituent of said form. It will be clear also, that the an.- thraquinone nucleus may v-be further substituted by simple or auxochromic substituents, such as hydroxy, methyl, methoxy, nitro, chloro, ar-ylaminovand the like, or it may be substituted: by complex substituents which in themselves may possess chromophoric configurations, such as the acridone ring, the xanthone ring, the benzoylamino group and the like.

The following examples illustrate but do not limit our invention. The parts are by weight.-

V 7 Example 1 22 parts of 2,2-dinitro-4,4 edicarboxy-diphenyl-'disu1fide, -;15 parts of thionyl, chloride and 200parts of nitrobenzen-e are warmed with stirring at 100-110 C, under reflux for 20hours. After this time, the acid chloride which has formed has dissolved to a clear solution in the nitrobenzene. 22 partso fl -amino-anthraquinone are now added andthe mixture is stirred, for 21/ hours at l 30.135 C, Hydrochloricacid is evolvedand the mixture thickens.- After cooling to 40 C, the yellow orystalline mass is cfilteredofi and washed successively with nitrobenzene and alcohol.

The so-obtained compound is treated at 30 0. 1 /2 u wit 0.0 s-0f e xszfi B 5 0f 33% causticsoda solution and 120 parts of sodium hydrosulfite, a clear solution being formed. 80

pa ts of sod um ch o w e a e er nqw-r idedahd NH-O 06401110 0 ON;

, l V n It may be applied to the fiber as described in themanner referred to above. As an illustration, the following method is given:-

-0.8 parts of dyestuff powder are dissolved in 400 parts of boiling water, and 8 parts of well wetted woolare added, followed by 8 parts of a 10% solution ofGlaubers salt. The solution is boiled for 1 hour, after which the fiber is removed, rinsed in cold water, and entered into a boiling solution of 10 parts of 7% aqueous hydrochloric acid and 200 parts of water; After 15 minutes the lactamizaa tion is complete and the fiber is rinsed in dilute sodium carbonate and dried. The wool is dyed orange yellowwhich on lactamization changes to a pure yellow, exceptionally fast to washing and potting.

Example 2 '22 parts of 2,2'-dinitro-4,4'-dicarboxy-diphenyl-disulfide are treated as described in Example 1 to give a solution of the acid chloride. 25 parts of '1-amino-4-methoxy-anthraquinone are added and the mixture is stirred at 130135 C. for hour and finally at 190 C. for some minlutes. On cooling, orange red crystals separate, which are filtered and washed with alcohol. The product is converted to the Water soluble dyestuff as described in Example 1. This is a bluish red powder soluble in warm water to an orange solution.

Wool is dyed in orange shades which on lactamizationchange to orange scarlet. The lactamized shade is of excellent fastness to washing and potting, in this respect being considerably superior tothe unlactamized shade.

Example 3 By substituting for the l-amino-l-methoxyanthraquinone of Example an equivalent weight of 1-amino-4-hydroxyanthraquinone, and carrying outthe sameseries of operations, 'a product is' obtained which after lactamization on Wool gives an orange scarlet shade similar to that of the dyestuff described in Example 2.

1 Example 4 operations, an orange yellow powder is obtained having the constitution ElNflOQ l NH. Hie-coma When applied to the fibre and lactamized it gives shades similar tothose of the product described in Example 1.

Example 6 By substituting for the l-aminoanthraquinone 0 of Example 5 an equivalent weight of l-aminolmethoxyanthraquinone, a dyestuff is obtained which on application to wool and lactamization yields a bright scarlet shade of excellent fastness to potting.

,7 Example7 ,7 p Y By substituting for the l-aminoanthraquinone 'of Example 1 an equivalent amount of l-amino- Echloroanthraquinone} a dyestuff is obtained which yields on lactamization a redder shade of yellow than that of the product of Example 1.

En temple 8 By substituting for the l-aminoanthraquinone of Example 1 an equivalent amount of l-amino-imethylaminoanthraquinone,- a dyestuff is obtained which gives blue-violet shades onwool, changing on lactamization toa reddish blue.

It will be understood that many 'variations and modifications are possible in our preferred mode of procedur'e'as above set forth, without departing from the spirit of this invention.

We claim: j 1

1I'A dyestuff compound of the general formula 11;;

, ,Nmo)

A-NHG O-aryl SdHr-COOM 2 a where A stands for the radical of an anthraquinone compound, while M stands for hydrogen or a metallic atom or radical.

2. Animal fiber dyed with the lactam of a compound asdefined in claim 1.

13. A compound of the'general formula A-Nre-ooOs-oHr-ooo wherein A stands for an anthraquinone nucleus, and M stands for hydrogen or a metallic atom orradical.

4. Animal fiber dyed with the lactam of a compound as defined in claim 3.

5. An intermediate for dyestuffs corresponding to the chemical'structure v ANHCOaryl a sire wherein A stands for the radical of an anthraquinone compound.

' 6. An intermediate for dyestuifs corresponding to the general formula A-NH-C 0-8ry]S's-8.l'Z1-C H 'A.

7 N05 oz 7 wherein A stands for the radical of an anthraquinone compound.

7. The process of preparing a dyestufi intermediate which comprises reacting an amino anthraquinone with the acid chloride of a dinitrodiaryl-disulfide-dicarboxylic acid, in which the nitro groups are in ortho position to the --SS-- linkage.

8. The process of preparing a dyestuff intermediate which comprises reacting an amino anthraquinone with the acid chloride of a dinitrodiaryl-disulfide-dicarboxylic acid, in which the nitro groups are in ortho position to the SS- linkage, and reducing the compound thus obtained to the ortho-amino-mercaptan form.

9. The process of preparing a dyestuff intermediate which comprises reacting an amino anthraquinone with the acid chloride of a dinitrodiaryl-disulfide-dicarboxylic acid, in which the nitro groups are in ortho position to the SS-- linkage, reducing the compound thus obtained to the ortho-aminmmercaptan form, and reacting upon the latter body with a halogeno-acetic acid.

10. The process of preparing a dyestuif compound which comprises reacting a lactam carboxylic acid compound as obtainable by dehydrating a carboxy ortho amino aryl thioglycollic acid, with an amino-anthraquinone compound, to form the corresponding aroyl-amino-anthraquinone derivative.

11. The process of preparing a dyestuff compound which comprises reacting a lactam carboxylic acid compound as obtainable by dehydrating a carboxy-ortho-amino-aryl-thioglycollic acid, with an amino-anthraquinone compound, to form the corresponding aroyl-aminoanthraquinone derivative, and hydrolyzing the product to transform it again into, the orthoamino-thioglycollic acid form.

NORMAN HULTON HADDOCK. FRANK LODGE. COLIN HENRY LUMSDEN. 

